Beta-hydroxyalkylcarbamyl-methylated aminotriazines

ABSTRACT

Novel beta-hydroxyalkylcarbamylmethyl aminotriazines function in self-condensation and as cross-linkers for amino resins and also compounds containing active hydrogen groups. The compositions cure to coatings with excellent properties, and they can be used as binders for fillers such as insulating glass and foundry sand.

This is a division of application, Ser. No. 06/864,626, filed May 16,1986, now U.S. Pat. No. 4,708,984.

The present invention relates to curable compounds and compositions andto methods of making and using them. More particularly, the presentinvention relates to novel beta-hydroxyalkylcarbamylmethylaminotriazinecompounds and to curable compositions comprising the novelbeta-hydroxyalkylcarbamylmethylaminotriazine, optionally, an activehydrogen-containing material or an amino resin, and, optionally, a curecatalyst. Coatings cured from the compositions have exceptionalresistance to detergent and salt spray exposure and improved solventresistance, making them well adapted for use in powder coatings, coilcoatings and can coatings. The curable compositions also act asefficient binders for fillers, such as glass and foundry sand.

BACKGROUND OF THE INVENTION

Curable compositions containing aminotriazine compounds are known in theart. As is shown in Koral et al., U.S. Pat. No. 3,661,819, for example,a preferred family of aminotriazine curing agents comprises (i) atriaminotriazine compound of the formula: ##STR1## which will bedepicted hereinafter as C₃ N₆ (CH₂ OR)₆ ; or (ii) a benzoguanaminecompound of the formula: ##STR2## which will be depicted hereinafter asC₃ H₅ (C₆ H₅)(CH₂ OR)₄ wherein R is hydrogen or alkyl of from 1 to 12carbon atoms. It is also known to use oligomers of such compounds, whichare low molecular weight condensation products containing for exampletwo, three or four triazine rings, joined by --CH₂ OCH₂ -- linkages, aswell as mixtures of any of the foregoing. These are used toself-condense or used to cure active hydrogen-containing materials,especially polymers which contain carboxyl groups, alcoholic hydroxygroups, amide groups and groups convertible to such groups, such asmethylol groups, as well as amino resins, such as hydroxymethylatedmelamine, urea, benzoguanamine, phenol and oligomers thereof, as well asmethylated, ethylated and butylated ethers thereof. When such curablecompositions are applied to substrates as coatings or used as bindersfor glass fibers or for foundry sand, and then cured, excellentproperties in terms of hardness, solvent resistance, tensile strength,etc., are imparted to the articles.

It has now been discovered that if aminotriazines of general formulae(i) and (ii) are reacted with betahydroxyalkyl urethanes, derivativesare formed which are also reactive to self-condense and to crosslinkamino resins and/or active hydrogen-containing polymers, but the newcoatings which are formed have much improved properties, e.g.,detergent, salt spray, adhesion, color retention and especially abrasionresistance and hardness over those of the prior art. When used asbinders, e.g., for glass or for fine sand, shaped articles are producedwhich have high tensile strengths and less tendency to emit formaldehydein use, making them highly suitable for use as insulation and as foundrycore molds.

Although it is known, e.g., from Valko, U.S. Pat. No. 4,435,559, to usebeta-hydroxy urethanes as cross linkers for active hydrogen containingcompounds, none of these prior art compounds are aminotriazinederivatives, and no property enhancement appears to have beenachieved--merely lower curing temperatures.

It is also known to produce hydroxy-functional melamine derivatives by,for example, reaction of melamine with propanolamine, e.g.,hydroxypropyl-functional melamine. Hydroxy alkyl carbamate functionalmelamine derivatives can also be made by reacting cyanuric chloride withthe adduct of diethylenetriamine and propylene carbonate.

It has also now been discovered that the reaction of hydroxyalkylcarbamates with alkoxymethyl or hydroxymethyl melamines andbenzoguanamines is very easily accomplished. The reaction productsformed are unexpected, in that the amino group of the beta-hydroxyalkylcarbamate reacts exclusively with the alkylol ether groups of theaminotriazine to give a blocked isocyanate having terminal hydroxylgroups. Of great interest, no crosslinked product is formed in thispreparation. Such an economical synthesis provides the novelmultifunctional compounds of this invention, containing wide ranging yetpredictable amounts of urethane linkages, reactive hydroxyl groups, andblocked isocyanate moieties for further elaboration.

In addition to their functions, mentioned above, in self-condensation orco-condensation to provide solvent-resistant, unusually hard coatings,further utility is found in reaction injection molding, e.g., withpolyisocyanates, and the like.

SUMMARY OF THE INVENTION

According to the present invention there are provided triazine compoundsselected from

(i) a triaminotriazine compound of the formula

    C.sub.3 N.sub.6 (CH.sub.2 OR).sub.6-x (CH.sub.2 NHCOOR.sup.1).sub.x ;

(ii) a benzoguanamine compound of the formula

    C.sub.3 N.sub.5 (C.sub.6 H.sub.5)(CH.sub.2 OR).sub.4-y (CH.sub.2 NHCOOR.sup.1).sub.y ;

(iii) an oligomer of (i) or of (ii) ; or

(iv) a mixture of at least two of any of (i), (ii) and (iii), whereinthe R groups are, independently, hydrogen or alkyl of from 1 to 12carbon atoms, the R¹ groups are, independently, beta-hydroxyalkyl offrom 2 to 18 carbon atoms, alone, or combined with alkyl of from 1 to 18carbon atoms, x is in the range of from about 3 to about 6, and y is inthe range of from about 2 to about 4.

In preferred embodiments of the invention, x is in the range of fromabout 5 to about 6 and y is in the range of from about 3 to about 4.With respect to compound (i) R is preferably methyl and R¹ isbeta-hydroxyethyl, beta-hydroxy propyl, e.g., a mixture ofbeta-hydroxy-alpha-methyl-ethyl and beta-hydroxy-beta-methylethyl, or amixture of beta-hydroxypropyl and n-octyl. Also preferred are oligomersof (iii)(i) in which R is methyl and R¹ is beta-hydroxyethyl orbeta-hydroxypropyl, as well as benzoguanamines (ii) wherein R is methyland R¹ is beta-hydroxyethyl or beta-hydroxypropyl.

Also contemplated by the present invention are curable compositionscomprising

(a) a triazine compound selected from

(i) a triaminotriazine compound of the formula C₃ N₆ (CH₂ OR)_(6-x) (CH₂NHCOOR¹)_(x) ;

(ii) a benzoguanamine compound of the formula C₃ N₅ (C₆ H₅)(CH₂OR)_(4-y) (CH₂ NHCOOR¹)_(y)

(iii) an oligomer of (i) or of (ii) ; or

(iv) a mixture of at least two of any of (i), (ii) and (iii), whereinthe R groups are, independently, hydrogen or alkyl of from 1 to 12carbon atoms, the R¹ groups are, independently, beta-hydroxyalkyl offrom 2 to 18 carbon atoms, alone, or combined with alkyl of from 1 to 18carbon atoms, x is in the range of from about 2 to about 6, and y is inthe range of from about 2 to about 4; and, optionally,

(b) an amino resin or an active hydrogen-containing material; and,optionally,

(c) a cure catalyst.

In preferred features of this aspect of the invention, the material (b)is an amino resin containing hydroxymethyl or methoxymethyl groups, andpreferably comprises a methylolmelamine or a methoxymethylolmelamine,and the polymeric material contains at least two reactive carboxyl,alcoholic hydroxy or amide groups, or a mixture of such groups,preferably a hydroxy-functional acrylic resin or a low molecular weightpolyester polyol. Preferably the triazine will be as set forthspecifically above, and the cure catalyst, if used, will be an acid,preferably p-toluenesulfonic acid, although it should be understood thatmany amino resins contain enough catalyst, e.g., residual acid catalyst,to make it unnecessary to add a cure catalyst separately. Othercatalysts suitable for this purpose are quaternary ammonium hydroxidesand organotin compounds.

Alternatively, the beta-hydroxy alkylcarbamylmethyl triazines can beused as a self-crosslinkable material in providing protective and/ordecorative coatings and binders.

Also provided by the invention are articles of manufacture comprisingsubstrates protectively coated with a baked and cured composition asdefined above and articles of manufacture comprising fillers and/orreinforcements, such as glass, mineral fillers, sand, especially foundrymold sand which has been treated with the curable composition definedabove, and then consolidated under heat into any desired shape.

DETAILED DESCRIPTION OF THE INVENTION

As starting materials to produce the beta-hydroxyalkylcarbamylmethylated triazines of this invention, there can be usedthe hydroxymethyl or alkoxymethyl melamines and/or benzoguanamines andoligmers thereof known in the art. Many of the starting materials arecommercially available, and can be made by well known procedures. Inaccordance with the present invention, the starting materials arereacted with beta-hydroxy alkyl carbamates, such as beta-hydroxypropylcarbamate, alone, or in admixture with alkyl carbamates in the presenceof an acid catalyst.

The beta-hydroxyalkyl carbamates are made, for example, by reacting acyclic propylene carbonate with ammonia: ##STR3## wherein R² ishydrogen, alkyl of from about 1 to about 16 carbon atoms. Depending onthe manner in which the ring is opened, R² will be alpha- orbeta-oriented with respect to the carbamyl function. The cycliccarbonates are made in known ways from the corresponding known1,2-diols, which are illustrated, for example, in the Valko patent, andinclude, for example, 1,2-polyols ranging in molecular weight from about62 to 286, typically ethylene glycol, 1,2-propylene glycol,1,2-butanediol, 1,2-hexanediol, and the like, up to 1,2-octadecanediol.

An idealized reaction equation for the preparation of the new compoundsfrom an alkoxymethylmelamine or a hydroxymethylmelamine is as follows:##STR4## wherein R, R¹ and x are as defined above.

The mole ratio of beta-hydroxyalkyl carbamate is selected to provide thedesired degree of substitution. By way of illustration, from 3 to 6moles can be used. If less than 3 moles are used, per mole of melaminecompound, premature gelation can be a problem. Reaction is typicallycarried out by heating in the melt or in solution, e.g., in benzene,toluene, xylene, chlorobenzene, dichlorobenzene, e.g., in the presenceof catalytic amounts of acid, e.g., para-toluene sulfonic acid, attemperatures between 70° and 150° C., preferably 75°-120° C. Measurementof the quantity of alcohol (ROH) evolved gives an indication of reactioncompletion. With 6 moles of beta-hydroxy alkyl carbamate, reaction isusually not 100% complete, unless forced, but a high degree ofsubstitution, x=5-6, is obtained. Analysis by gel permeationchromotography shows that treatment of hexamethoxymethylolmelamine withsubstantially less than 6 moles of beta-hydroxy alkyl carbamate gives aproduct which contains a similar oligomeric distribution as thetriamino-triazine reactant comprised of a mixture of compounds withdegrees of substitution ranging up to 6. 0f course, only those compoundswherein two carbamylmethyl groups are present are crosslinkers accordingto this invention, even though residual alkoxymethyl groups can providecrosslinking.

Instead of alkoxymethylmelamines, hydroxymethylmelamines, and thecorresponding benzoguanamine analogs and oligomers can be used asstarting materials. With benzoguanamines, it is believed that if lessthan 2 moles of hydroxyalkyl carbamate is used per mole of triazine,premature gelation may be encountered. The products can be recovered byany convenient means after removal of byproduct water or alcohol iscomplete. Simply cooling them to room temperature will leave the productas a residue, and the acid catalyst can be removed by neutralization.

The substituents defined by R and R¹ in the formulae above can varywidely in carbon content, and the groups can be straight chain, branchedchain and alicyclic. Representative compounds will be exemplifiedhereinafter.

The active hydrogen-containing materials have as the active hydrogengroup a group selected from carboxyl, alcoholic hydroxyl, amido, primaryamine, secondary amine (including imine), thiol and the like. The activehydrogen-containing materials useful herein are typically film-formingcompositions. Illustrative examples of active hydrogen-containingmaterials are shown in the above-mentioned Koral patent, GermanPublished Patent Application OLS 2,055,693, and in the above-mentionedValko Patent. Typical polymers are acrylic polymers, polyesters, epoxyresins, and the like, providing that they contain active hydrogengroups.

Especially suitable are polyesters and polyacrylates containing pendanthydroxyl groups as reaction sites. The former are obtained in a knownmanner by the reaction of polycarboxylic acids with excess quantities ofpolyhydric alcohols; the latter are obtained by the copolymerization ofacrylic or methacrylic acid derivatives with hydroxyl-group-containingderivatives of these acids, such as, for example, the hydroxyalkylesters, optionally with the simultaneous use of additional vinylcompounds, such as, for example, styrene, or by the polymerization ofcaprolactone. Hydroxyl-group-containing polyurethanes can be obtained inknown manner by the reaction of polyisocyanates with excess quantitiesof compounds containing at least two hydroxy groups. Suitablecommercially available hydroxy-group-containing polyesters are CYPLEX®1473 and CYPLEX® 1531 from American Cyanamid Company and CargilPolyester 5776, and from Union Carbide Corp. under the trademark TONE®0200. Suitable hydroxy-functional acrylic resins are availablecommercially from S. C. Johnson & Son, Inc. under the trademark JONCRYL®-500, and Rohm & Haas Co., under the trademark AT-400. Also suitable foruse are the copolymer of 50% styrene, 2O% hydroxypropyl methacrylate and30% butyl acrylate of Example 5 of the above-mentioned German OLS2,055,693 and the polyester of phthalic acid, adipic acid, ethanediol,and trimethylolpropane, with a hydroxy number of 130 and an acid numberof 1.5 of Example 6 of the said OLS publication.

As set forth herein, the curable composition includes a cure catalyst;when appropriate--amino resins can cure with heat alone, because theyusually contain residual acid catalyst. Typically, the cure catalyst isan acid which is soluble in the composition, such as a mineral acid,e.g., hydrochloric or nitric acids or an organic acid, such asp-toluenesulfonic acid or a naphthalene sulfonic acid, all of which arewell known to those skilled in this art. The cure catalyst is used inamounts effective to accelerate cure at the temperatures employed, e.g.,120°-220° C. For example, the catalyst is used in amounts from about 0.1to about 2.0 preferably 0.2 to 1% by weight based on the weight of thecurable compositions. Quaternary ammonium hydroxides have also been usedas catalysts in the same concentration range.

In the practice of the invention, the curable compositions can beadapted for use in solvent-based or water-based coating or bindercompositions. Coating compositions comprising aqueous dispersions areparticularly suited to application by electrodeposition. Generally thecompositions will contain about 1 to 75 percent by weight of resin andnovel aminotriazine combined, and the weight ratio of novelaminotriazine to resin will range from about 5 to about 40 parts tocorrespondingly from 60 to 95 parts of said resin.

In many instances a pigment composition and various conventionaladditives such as antioxidants, surface active agents, coupling agents,flow control additives, and the like, can be included. The pigmentcomposition may be of any conventional type, such as, one or morepigments such as iron oxides, lead oxides, strontium chromate, carbonblack, titanium dioxide, talc, barium sulfate, cadmium yellow, cadmiumred, chromic yellow, or the like.

After deposition on a substrate, such as a steel panel, the coatingcomposition is devolatilized and cured at elevated temperatures by anyconvenient method such as in baking ovens or with banks of infrared heatlamps. Curing can be obtained at temperatures in the range of from 120°C. to about 300° C., preferably from 150° C. to about 200° C. for fromabout 30 minutes at the lower temperatures to about 1 minute at thehigher temperatures.

Alternatively, the new aminotriazines can be added to varnishescomprising, for example, amino resins, such as methylolated ureas, andmelamines and used to impregnate surface sheets for laminatesconsolidating under heat and pressure using conventional conditions toproduce laminates. They can also be formulated with normallythermoplastic hydroxyl group-containing polyurethanes and injectionmolded during which they react and cure in the mold to RIM(reaction-injection-molded) articles of manufacture.

By entirely conventional methods, the new compounds can be used inbinder compositions for fillers and/or reinforcements ordinarily usedwith amino resins, such as cellulose, wood or paper flour or fibers,minerals such as talc, asbestos, wollastonite, silica, metals, such assilver, nickel, or non metals, such as carbon, and glass powder orfibers, textiles and sand, such as foundry sand.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following examples illustrate the compounds and compositions of thepresent invention. They are not to be construed as limiting the claimsin any manner. All parts are by weight.

EXAMPLE 1 Reaction Product of 6 Moles of Hydroxypropyl Carbamate With 1Mole of Hexamethoxymethylmelamine

Hexamethoxymethylmelamine (81.9g, 0.21 mole, American Cyanamid Co.CYMEL® 300), hydroxy-propyl carbamate (150.0 g, 1.26 mole), andpara-toluenesulfonic (1.16 g) are stirred at 75° C. in a flask equippedwith a vacuum distillation head. During 80 minutes, the pressure islowered in stages to 50 mm Hg and 37.2 g of methanol (1.02 mole, 81% oftheoretical) is collected in the distillate receiver. The product in thereaction flask is cooled to near room temperature, where it is a clear,colorless, glass which is soluble in methanol, ethylene glycol or water.The product is of the formula:

    C.sub.3 N.sub.6 (CH.sub.2 NHCOOC.sub.3 H.sub.6 OH).sub.6

EXAMPLES 2-5

If the general procedure of Example 1 is repeated, substituting analogsof beta-hydroxypropylcarbamate, the followingbeta-hydroxyalkylcarbamylmethyl melamines will be obtained:

    ______________________________________                                        C.sub.3 N.sub.6 (CH.sub.2 NHCOOR.sup.1).sub.3-6                               Example                                                                              R.sup.1                                                                ______________________________________                                        2      CH.sub.2 CH.sub.2 OH   --                                                      ##STR5##        +                                                                                    ##STR6##                                       4                                                                                     ##STR7##        +                                                                                    ##STR8##                                       5                                                                                     ##STR9##        + +                                                                                  ##STR10##                                      ______________________________________                                    

EXAMPLE 6 Reaction Product of 5.25 Moles of Hydroxyethyl Carbamate With1 Mole of Hexamethoxymethylmelamine Oligomer

A mixture of 221.45 g, 0.607 mole of oligomeric methlolmethylatedmelamine (CYMEL® 303, American Cyanamid Co.), 334.45 g, 3.1852 moles ofbeta-hydroxyethyl carbamate and 0.99 g of conc. nitric acid is heated at100° C. under a constant nitrogen flow. Vacuum is then applied tomaintain a constant distillation of methanol. The maximum vacuum appliedis 50 mm Hg. The reaction is stopped after 50 minutes.

The product is recovered by dissolving the reaction mixture in watercontaining one equivalent of base to neutralize the acid catalyst and toprovide a solution containing 45% solids, by weight. The product is ofthe formula:

    C.sub.3 N.sub.6 (CH.sub.2 NHCOOCH.sub.2 CH.sub.2 OH).sub.5.25 (CH.sub.2 OCH.sub.3).sub.0.75

EXAMPLE 7 Reaction Product of 2 Moles of n-Octyl Carbamate and 4 Molesof Hydroxy-Propyl Carbamate With 1 Mole of Hexamethoxymethyl Melamine

Hexamethoxymethyl melamine (13.5 g, 0.0346 mole) and 12.0 g (0.0694mole) of n-octyl carbamate are stirred at 75° C. in a flask equippedwith a vacuum distillation head and a receiver cooled in dryice-acetone. Then 0.18 g (0.0010 mole) of p-toluenesulfonic acid isadded. During 50 min., the pressure is lowered in stages to 50 mm. Hgand 2.36 g of methanol (0.0738 mole, 106% of theoretical) is collectedin the receiver. Gas chromatography of the reaction mixture showscomplete consumption of the n-octyl carbamate.

Then 16.5 g (0.139 mole) of hydroxypropyl carbamate is added. During 70min., the pressure is lowered in stages to 50 mm Hg and 3.86 g ofmethanol (0.121 mole, 87% of theoretical) is collected in the receiver.

After cooling to room temperature, the reaction product is a colorlessnear-solid. It is dissolved in 150 ml of methylene chloride by stirringfor 45 min. at room temperature. The solution is washed in a separatoryfunnel with two 50 ml portions of 5% Na₂ CO₃ solution, and dried overanhydrous granular K₂ CO₃. Rotary vacuum evaporation affords 44.2 g (96%theoretical yield) of a moderately viscous liquid which is easilydissolved at 75% solids concentration in methyl isobutyl ketone to givea colorless, mobile solution. The product is of the formula:

    C.sub.3 N.sub.6 (NHCOOC.sub.8 H.sub.17).sub.2 (CH.sub.2 NHCOOC.sub.3 H.sub.8 OH).sub.4

EXAMPLE 8

If the general procedure of Example 1 is repeated, substituting anoligomeric methylolated melamine methyl ether (American Cyanamid Co.,CYMEL® 303), the corresponding beta-hydroxy propylcarbamylmethylatedoligomeric melamine of this invention will be obtained.

EXAMPLE 9

If the general procedure of Example 1 is repeated, substituting atetramethoxymethylolbenzoguanamine (American Cyanamid Co., CYMEL® 1123),the corresponding beta-hydroxy-propylcarbamylmethylated benzoguanamineof this invention will be obtained.

In the following examples, the beta-hydroxy alkyl-carbamylmethylatedtriazines of this invention are formulated into curable compositions andevaluated as coatings.

Procedure for Coatings Preparation

The hexa(hydroxypropylcarbamylmethyl) melamine is used as a 75% solutionin methanol and thetetra(hydroxypropylcarbamylmethyl)di(n-octyl-carbamylmethyl) melamine isused as a 65% solution in methyl isobutyl ketone. The polymericcomponents are supplied as 60% to 100% solids.

The formulated coatings are made up at 55-65% solids by dilution toappropriate viscosity with solvents such as n-butanol or MIBK.

The coatings are drawn down on 4"×12"×12 ga. BONDERITE® 100-treatedsteel panels (from Parker Chemical Co.) by using a wire-wound applicator(WIRE-CATOR®). In some cases FC-431 (3M Co.), a fluorochemicalsurfactant, is added to the formulation to improve flow-out. Afterstanding for a few minutes at room temperature to improve leveling, thepanels are placed horizontally in a pre-heated forced-draft air oven forcuring at the appropriate time and temperature. Solvent resistance isused as the screen for curing completeness. The 70° C. DetergentReistence is measured by ASTM D714, rated on a scale of 1-10; 10 meansno blistering. Salt Spray Resistance is by ASTM D1654. Taber Abrasion ismeasured by ASTM D4060. Forward and Reverse Impact Strength is measuredby ASTM D-3281.

EXAMPLES 10-13

The crosslinker of Example 1 herein, the reaction product of 6 moles ofbeta-hydroxypropyl carbamate and 1 mole of hexamethoxymethyl melamine isused with a methoxymethyl melamine oligomer and p-toluenesulfonic acidas cure catalyst. The formulations used and the properties of the curedfilms are set forth in Table 1:

                  TABLE 1                                                         ______________________________________                                        Hydroxyalkylcarbamyl                                                          Methyl Melamine Cured With                                                    Melamine Resin                                                                Example          10       11     12     13                                    ______________________________________                                        Composition (parts by weight)                                                 6-beta HOPC.sup.a                                                                              70       70     50     30                                    Melamine Resin.sup.b                                                                           30       30     50     70                                    p-TSA.sup.c       1        1      1      1                                    Cure Temp., °C.                                                                         125      150    125    125                                   Cure Time, min.  30       20     130    130                                   Properties                                                                    MEK Resistance.sup.d                                                                           P        P      P      P                                     Methanol Resistance                                                                            P        P      P      P                                     Knoop Hardness   57       40     25     25                                    Reverse Impact, in. lbs.                                                                        5       --      5      5                                    ______________________________________                                         .sup.a beta-hydroxypropylcarbamylmethyl melamine (Example 1);                 .sup.b CYMEL ® 303, American Cyanamid Co.;                                .sup.c p-Toluenesulfonic acid; and                                            .sup.d P = Passes 200 double rubs.                                       

EXAMPLES 14-19

The reaction products of Example 1 and 7 herein, are used with ahexamethoxymethyl melamine oligomer resin and a reaction product of 2moles of n-octyl carbamate and 1 mole of hexamethoxymethyl melamineusing p-toluenesulfonic acid as cure catalyst. An epoxy resin, aglycidyl ether of bisphenol-A, EPON® 1001, Shell Chemical Co., isincluded in some of the formulations. The formulations used and theproperties of the cured coatings are set forth in Table 2:

                  TABLE 2                                                         ______________________________________                                        Hydroxyalkylcarbamyl-                                                         methylated Melamine Cured                                                     Resin Coatings                                                                Example     14     15     16   17    18    19                                 ______________________________________                                        Composition (parts                                                            by weight)                                                                    Hexa(hydroxy-                                                                             40     30     30   --    --    --                                 propylcar-                                                                    bamylmethyl)                                                                  melamine                                                                      Tetra(hydroxy-                                                                            --     --     --   60    50    33                                 propylcar-                                                                    bamylmethyl)di( -n-                                                           octylcar-                                                                     bamylmethyl)                                                                  melamine                                                                      Hexa(methoxy-                                                                             --     --     --   40    50    67                                 methyl)                                                                       melamine                                                                      Tetra(methoxy-                                                                            40     35     30   --    --    --                                 methyl)di(n-octyl-                                                            carbamyl-                                                                     methyl) melamine                                                              EPON ® 1001,                                                                          20     35     40   --    --    --                                 epoxy resin                                                                   p-Toluenesulfonic                                                                          1      1      1   0.5   0.5   0.5                                Acid                                                                          FC-431(fluoro-                                                                            --     --     --   0.1   0.1   0.1                                chemical                                                                      surfactant)                                                                   Cure, °C./min.                                                                     150/   150/   150/ 125/  125/  125/                                           20     20     20   20    20    20                                 Properties                                                                    MEK Resistance                                                                            P      P      P    P     P     P                                  Knoop Hardness                                                                            12     15     17   16    16    16                                 Reverse Impact,                                                                             5     5      5   5     5     5                                  in. lbs.                                                                      Forward Impact,                                                                           15     15     15   15    15    15                                 in lbs.                                                                       70° C. Detergent,                                                                  --     --     --   40/10 40/10 40/10                              hrs./blist. rating                                                            ______________________________________                                    

Excellent coatings are obtained in accordance with this invention.

EXAMPLES 20-25

The reaction products of Examples 1 and 7 herein are used with ahexamethoxymethyl melamine oligomer resin to crosslink severalcommercially available hydroxy functional polymers. An epoxy resin,EPON® 1001 is included in some of the formulations. The formulationsused and the properties of the cured coatings are set forth in Table 3,as follows:

                  TABLE 2                                                         ______________________________________                                        Hydroxyalkylcarbamyl-                                                         methylated Melamine Crosslinked                                               Acrylic and Caprolactone Resins                                               Example     20     21     22    23    24    25                                ______________________________________                                        Composition                                                                   (parts by weight)                                                             Hexa(hydroxy-                                                                             15     10     35    20    --    --                                propylcar-                                                                    bamylmethyl)                                                                  melamine                                                                      Tetra(hydroxy-                                                                            --     --     --    --    31    33                                propylcar-                                                                    bamylmethyl)di( -n-                                                           octylcarbamyl-                                                                methyl)melamine                                                               Hexa(methoxy-                                                                             15     10     25    25    33    42                                methyl)melamine.sup.a                                                         AT-400(hydroxy-                                                                           70     80     --    --    --    --                                functional)                                                                   polyacrylate.sup.b                                                            JONCRYL ® 400                                                                         --     --     40    55    --    --                                (hydroxyfunctional)                                                           polyacrylate.sup.c                                                            TONE ® 0200                                                                           --     --     --    --    --    15                                (polycaprolactone                                                             diol).sup.d                                                                   EPON ® 1001,                                                                          --     --     --    --    14    10                                epoxy resin.sup.e                                                             p-Toluenesulfonic                                                                          1      1     0.5   0.5   0.5   0.5                               Acid                                                                          FC-431(fluoro-                                                                            --     --     0.1   0.1   0.1   0.1                               chemical surfactant)                                                          Cure, °C.                                                                          125    125    125   125   125   125                               Cure Time, min.                                                                           20     20     20    20    20    20                                ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Example     20     21     22    23    24    25                                ______________________________________                                        Properties                                                                    MEK Resistance                                                                            P      P      P     P     P     P                                 Knoop Hardness                                                                            13     9.3    18    15    14    12                                Reverse Impact,                                                                           10     10     5     5     5-10  15                                in. lbs.                                                                      Direct Impact,                                                                            --     --     20-30 20-30 30    50                                in. lbs.                                                                      70° C. Detergent,                                                                  --     --     24/rust                                                                             24/D6 96/10 96/                               hrs./Blister Rating                         M8                                Salt Spray, Hrs./                                                                         --     --     96/2  96/7  --    --                                Creepage (mm)                                                                 Taber Abrasion, mg                                                                        --     --     45    47    67    17                                lost/cycle × 1000                                                       ______________________________________                                         .sup.a American Cyanamid Co.                                                  .sup.b Rohm & Haas & Co.                                                      .sup.c S. C. Johnson & Sons, Inc.                                             .sup.d Union Carbide Corp.                                                    .sup.e Shell Chemical Co.                                                     .sup.f 3M Co.                                                            

Excellent coatings are obtained in accordance with this invention.

A review of the data in the foregoing tables indicates that excellentproperties are obtained with the beta-hydroxy alkylcarbamylmethylatedtriazines of this invention.

It is generally the case also, that thebetahydroxyalkylcarbamylmethylated melamines of this invention affordcoatings with good color stability. Finally, the data show that whileoutstanding resistance properties and color stability have been obtainedwith the betahydroxyalkylcarbamate melamines, other important anddesirable coatings properties such as Knoop hardness, impact and solventresistance (MEK rubs +200) have been maintained as is the case withconventional resins.

The hydroxyalkylcarbamylmethylated-melamines and -benzoguanamines ofthis invention are useful as binders for fillers and/or reinforcements,e.g., mineral and glass fillers as is illustrated by the followingexamples.

EXAMPLE 26-27

A binder formulation for fiberglass insulation is prepared and screenedin a standard test by binding very fine glass beads in a dogbone shapedbonded test piece. The tensile strength of the test piece is thendetermined by a standard method.

The binder formulation comprises:

1.33 parts by weight of a 75 wt. % solution of 6-HOPC (the product ofExample 1);

8.00 parts of 25 wt. % aqueous low molecular weight starch (RAISIO®K-55);

0.60 parts additional water; and

0.60 parts of 10% phosphoric acid in water.

The mixture is thoroughly blended with 60 parts by weight of fine glassshot and pressed into two dogbone shaped molds. The pieces are removedfrom the mold and cured in an oven at 140° C. for 60 minutes. The curedcoatings (1/4×1" cross section at neck) are found to have tensilestrengths of 80 and 110 lbs. (320 and 440 psi) compared to 0 psi with nobinder and 10-30 psi for poor binder formulations.

If foundry sand is substituted for glass and coated with thehydroxypropyl carbamylmethylated melamine of this invention, starch andacid, the coated sand will cure into foundry molds eminently suitablefor metal casting (little or no formaldehyde odor is detectable uponexposure to foundry temperatures).

The above-mentioned patents and publications are incorporated herein byreference. Many variations of this invention will suggest themselves tothose skilled in this art in light of the above, detailed description.For example, instead of reacting hexamethoxymethylmelamine or anoligomer with beta-hydroxypropylcarbamate,tetramethoxymethylbenzoguanamine can be reacted withbeta-hydroxypropylcarbamate to obtain a crosslinker according to thisinvention. Instead of using beta-hydroxypropylcarbamylmethylatedmelamine as curing agents in the formulations of Tables 1-3, thecorresponding beta-hydroxy alkyl carbamylmethylated melamine andmelamine oligomers of Examples 2-6 can be used. Instead ofp-toluenesulfonic acid as cure catalyst, mineral acids, such ashydrochloric acid and nitric acid can be used. Instead ofhydroxyfunctional polyesters and polyacrylates, epoxy resins, such asthe polyglycidylethers of bisphenol A and the reaction products thereofwith amines and ammonia can be used. All such obvious modifications arewithin the full intended scope of the appended claims.

We claim:
 1. A triazine compound selected from(i) a triaminotriazinecompound of the formula

    C.sub.3 N.sub.6 (CH.sub.2 OR).sub.6-x (CH.sub.2 NHCOOR.sup.1).sub.x, or;

(ii) a benzoguanamine compound of the formula

    C.sub.3 N.sub.5 (C.sub.6 H.sub.5)(CH.sub.2 OR).sub.4-y (CH.sub.2 NHCOOR.sup.1).sub.y, or;

(iii) an oligomer of (i) or (ii),wherein the R groups are,independently, hydrogen or alkyl of from 1 to 12 carbon atoms, the R¹groups are, independently, beta-hydroxyalkyl of from 2 to 18 carbonatoms or alkyl of from 1 to 18 carbon atoms, wherein at least one R¹ isbeta-hydroxyalkyl, and x is in the range of from about 3 to about 6, anyy is in the range of from about 2 to about
 4. 2. A triaminotriazinecompound (i) as defined in claim 1 wherein x is in the range of fromabout 5 to about
 6. 3. A triaminotriazine compound (i) as defined inclaim 1 wherein R¹ comprises a mixture of beta-hydroxy-alpha-methylethyland beta-hydroxy-beta-methylethyl.
 4. A benzoguanamine compound (ii) asdefined in claim 1 wherein R is methyl and R¹ is beta-hydroxyethyl orbeta-hydroxypropyl.
 5. A triaminotriazine compound (i) as defined inclaim 1 wherein one or more of the R¹ moieties are selected from thegroup consisting of:(a) beta-hydroxyethyl, (b) beta-hydroxypropyl, and(c) a mixture of beta-hydroxyethyl and beta-hydroxypropyl.
 6. Anoligomer of a triaminotriazine compound of the formula:

    C.sub.3 N.sub.6 (CH.sub.2 OR).sub.6-x (CH.sub.2 NHCOOR.sup.1).sub.x

wherein the R groups are, independently, hydrogen or alkyl from 1 to 12carbon atoms, the R¹ groups are, independently, hydrogen, alkyl of from1 to 12 carbon atoms, the R¹ groups are, independently,beta-hydroxyalkyl of from 2 to 18 carbon atoms or alkyl of from 1 to 18carbon atoms, wherein at least one R¹ is beta-hydroxyalkyl, and x is inthe range of from about 3 to about
 6. 7. An oligomer of a benzoguanaminecompound of the formula:

    C.sub.3 N.sub.5 (C.sub.6 H.sub.5)(CH.sub.2 OR).sub.4-y (CH.sub.2 NHCOOR.sup.1).sub.y

wherein the R groups are, independently, hydrogen or alkyl from 1 to 12carbon atoms, the R¹ groups are, independently, beta-hydroxyalkyl offrom 2 to 18 carbon atoms or alkyl of from 1 to 18 carbon atoms, whereinat least one R¹ is beta-hydroxyalkyl, and y is in the range of from 2 toabout
 4. 8. Thecompoundbeta-hydroxypropylcarbamylmethylmelaminerepresented by theformula:

    C.sub.3 N.sub.6 (CH.sub.2 NHCOOC.sub.3 H.sub.6 OH).sub.6